Treatment of textile materials



Patented Sept. 10, 1935 UNITED STATES 2,013,689 TREATMENT or TEXTILEMATERIALS Ernest William Kirk and George Holland Ellis,

Spondon, near Derby, England, assignors to' PATENT ;=OFFICE CelaneseCorporation of America, a. corporation l of Delaware.

No Drawing. Application April 14,. 1933, Serial No. 66fi,173. In GreatBritain May 12, 1932 7 claims. (oi, s-s) This invention relates to'theproduction of colorations on textile materials and especially uponmaterials consisting of or containing cellulose acetate or othercellulose esters or ethers.

In the coloration of textile materials it is frequently found necessary,in order to obtain a particular shade or a particular shade of special'fastness or other property, to employ mixtures ofcoloring matters. Ingeneral however it is necessary procedures in the two cases.

I We have now found that valuable mixed shades may be obtained byapplying to or incorporating in textile materials a leuco compound of avat dyestuil, a 'diazotizableamine and an azo coupling component, andthereafter subjecting the '95 :iterial to treatment to effectdiazotization and coupling, and also the oxidation of the leuco compoundto the parent vat dyestuff.

Thus, for example, a cellulose acetate material may'be dyed in a greenshade by impregnating with a chloraniline anddiaceto-acetyl-orthotolidide and the leuco compound of a blue indigoiddyestufi and thereafter treating with nitrous acid in order todiazotizethe. amine and so eiIect coupling, and simultaneously tooxidize the leuco compound of the vat dyestuii. In this way the desiredmixed shades of vat and azoic colors may be obtained with little or nomore complication of procedure than is normally necessary in theproduction of azoic colorations on textile mate:

' rials. Moreover, the mixed shades obtainable exhibit a high degree offastness for the dyeings obtainable by vat or azoic methods in generalexhibit exceedingly good fastness properties.

The three components, diazotizable amine, coupling component and leucovat dyestufi, are conveniently applied to the material simultaneously Ifdesiredhowever they may be applied separately to the materials, thoughin general less nated material may be subjected to a mild oxidaacidbaths suitable for eifecting the diarptization from a single bathvpadding liquid the m -of the amines. When therefore these esters areemployed the treatment maybe similar to that tion, for example, by meansof air, in order to oxidize the leuco compound, "and thereafter to theaction of nitrous acid, followed if necessary by an alkaline treatment,in order to 'eifect diazotization and coupling. Mostconveniently how- 5ever the diazotization and oxidation of the leuco compound are effectedsimply by treatment in a nitrous acid bath, the nitrite serving-the dualpurpose of di'azotizing agent and oxidizing agent. Following the nitrousacid treatment the mate- 1 rials may be subjected to soaping, preferablyin the presence of sodium carbonate, or to other weakalkalinetreatmentto ensure completion of the coupling. Further, if desired, thematerial 'may be subjected to a mild oxidizing treatment 15 to ensurethe complete oxidation of the leuco compound of the vat dyestufi.

The diazo component, coupling component and leuco'vat dyestufi', may beapplied to the materials either in the free state or in the form ofsalts, 2 I

according to the character of the material under-.

going treatment and the precise method 01' application employed. Thus,in the case of celllilosic materials the coupling component and theleuco compound are advantageously applied in 25 the form of alkalisalts, in which form they exhibit very good aflinity for the material.In the case of animal fibres, for example wool .or silk, and. celluloseacetate or other cellulose ester or ether artificial silks, thecomponents are, with particular advantage, applied in the free state tothe materials. In this state the components exhibit very good affinityfor these materials, and in consequence dyeings .are obtained possessingvery good fastness to rubbing, in addition to other desirable fastnessproperties.

If desired leuco compounds of the vat dyestufis may be applied to orincorporated in the materials in the form of their sulphuric, phosphdricor other esters, for example the products sold under the name Indigosolor the registered trade-mark Soledon. These sulphuric or other esters ofthe leuco compounds are readily saponified and oxidized to the vatdyestufl by the nitrous 5 adopted when the leuco vat dyestuffs are em-'ployed in the free state or in the form of alkali '0 .metal salts.

7 'compounds.

1,844,350, Bri ish Patents 396,412 and 404,327.

Likewise coupling .components of widely .varying character may beemployed, for example any of those mentioned' in U. S. application S.No. 666,172, for example arylamides of 2:3-oxynaph- 'thoic acids.Particularly useful results may be diaceto-acetyl-orthotolidide andorthochloraniline. Again, purple shades may be obtained by using 5:7:5:7'-tetrabromindigo, 2:3-oxynaphthoic acid-m-nitranilide and5-nltro-2-aminoanisole;

The vat dyestuffs employed may be of any desired series, forexampleof-the anthraquinone or indigoid series. Further, sulphur dyestuffs maybe applied in accordance with the new process, and in fact any of thedyestufis or classes of dyestufl's referred to inU. S. Patent No.1,960,172 as suitable for application to jcellulose ester and ethermaterials in the form of their free leuco In the case of cellulose esteror ether materials, particularly useful results may be secured bymeansrof dyestuffs of the indigoid series,-or by means of anthraquino nedyestuffs containing only a single anthraquinone'nucleus.

Dispersions of the diazo or coupling components may be obtained by anydesired method for example, by fine milling or grinding with or withoutthe aid of dispersators and/or protective colloids, by'precipitation inthe presence 0f protective colloids, or by a simple treatment withdispersators, as described for instance in any of U. S.'Patents NOS.1,613,413, 1,618,414, 1,694,413,,

1,690,481, 1,803,008, 1,840,572, -1,716,721 and 1,928,647 and BritishPatent;No.-323,788. Disper sion of coupllng'components, especially thoseof phenolic character or containing the''C0.H:-

group may frequently be-facilitated by the presence of small quantitiesof alkali, for example, a;

quantity of caustic soda sufficient to yield a solution of about pH'7.2or even slightly more alkaline.

Vat dyestufis may be vatted' with caustic alkali anda reducing agent andapplied to the materials together with or separately from the diazo andcoupling components. In the case of animal fibres, cellulose esters orother materials liable to damage by alkali, the excess alkali of .thevat may be neutralized, for example by means of organic acids or theremay be used vats of relatively low alkalinity prepared with the aid ofammonia, organic amines or other weak alka- 'lies. Any such organicacids or organic bases 'f should of course be such as do not interferewith the pmduction of the deslredshades, e. g., by coupling with thediazo compound. Where the I leuco compounds are to be ap lied tothe-ma.-

terials in thefree state they are advantageously converted into finesuspensions or dispersions,

for example in any of the ways described in U. S.

Patent N0. 1,900,172. ri The various components, whether in free orcombined form, may be applied to the materials in any desired manner.Thus, for'instance,

they may be applied by dyeing, padding or other mode of .uniformapplication, 'or by printing,

stencilling' or other mode. of local'application. For padding, printingand the like the preparations containing the components may contain anydesired thickening or other agents to fit them 2,018,689 amines are givfor instance U. S. Patent No.

pfegnated with a mixture of diazotizable amine an dcoupling component,over-printed with a leuco compound of a vat dyestuff or an esterthereofand thereafter diazotized and developed.

In-this way a pattern colored by both dyestuffs" is obtained upon aground colored only by the (azoic colorations.

- As indicated previously the invention is of especial interest in thecoloration. of cellulose ester or ether materials. Such materials mayfor instance consist of the previously mentioned cellulose acetate or ofother cellulose esters or mixed esters, for example cellulose formate,propionate, butyrate,-'a nitroacetate, or acetate-butyrate, or cellulose'esters obtained by esterifying cellulose while retaining its fibrousform. Again, cellulose ethers, or ether-esters for instance ethyl orbenzyl cellulose may be colored. Other natural or artificial materials,for example animal fibres,

'cotton or the regenerated cellulose type of arti-- sisting of celluloseacetate and a cellulosic fibre 40 such as cotton ;or viscose artificialsilk, the acetate only may be colored by applying the components in thefree-state, under which conditions they possess little or no afiinityfor the cellulosic material.

The invention is illustrated the following examples:-

Ezamplei L but not limited by To, dye a brilliant emerald green shade on10 .50

kilograms of cellulose 'acetate'yarn.

300 grams -oi Algol brilliant green-BK paste (Schultze, 7th Edition;volume 2, page 6) are wetted down with methylated spirit and vatted inabout-30 litres of soft water at 60 C. by addition of 50 cos. ofmonoethanolainine and 100-grams of sodium hydrosulphite powder. Inandther vessel 100 grams of ortho-chloraniline are dispersed by heatingwith 200 grams of Turkey red oil and diluting with hot soft water. Boththese solutions are then added to' the dyebath, followed by a; solutionof 200 grams of diaceto-acetyl-orthotolidine in sufiicient hot softwater containing 40 grams of caustic soda. A solution of 100 grams ofglucose is then added and the bath adjusted to 300 litres. The yam'isentered into the dyebath at 30-40 C. and worked for half-an-hour, duringwhich time .the temperature of the bath is raised to 75 C. andthedyeing' continued at this temperature fora further hour. The yarn islifted, thoroughly rinsed 011; and entered in adi- L azotizationbathxcontainlng 8-grams per litre of glacial acetic acid and 4 grams perlitre of sodium nitrite, the temperature not exceeding 15 C. Afterworking in this bath for half-an-hour the yarn is again lifted andthoroughly rinsed, and then entered into a cold bath containing A gramper litre soda ash and 1 gram per litre good textile soap, worked coldfor a quarter of an hour, the temperature raised slowly to 75 C. andworked at this point for a further half hour. The yarn is then lifted,rinsed and dried, or otherwise treated as requisite.

Example 2 To. obtain a green printed design on a white ground ofcellulose acetate fabric.

The following paste is first prepared:-

1.6 parts 2:5-dichloraniline 3.8 Diacetoacetylorthotolidine. 6.0Indigosol blue AZG. 10.0 Ethyl lactate. 10.0 Diethylene glycol.

Gum arabic thickening to 100.0 parts Example 3 To dye a fast green shadeon 10 kilograms of silkyam.

100 grams of 5:7:5':7' tetrabromindigo are vatted by warming to C. with200 grams of monoethanolamine, 200 gramsTurkey red oil and 100 grams ofsodium 'hydrosulphite in 5 litres of soft water. 100 grams of2:5-dichloraniline are dispersed by warming with 300 cos;

of Turkey red oil and diluting with 1 litre of boiling soft water, and200 grams of (ii-acetoacetyl-orthotolidine are dissolved with 50 gramsof caustic soda and 5 litres of hot soft water. These dispersions arethen added to the dyebath which already contains 100 grams of glucoseand which-is adjusted to a volume of 300 litres, and the previouslydegummed silk yarn entered. The temperature is then slowly raised to 75C. and kept at this for an hour and a half the silk meanwhile being wellturned. The yarn is then lifted and rinsed, and entered directly intothe diazotiz ing bath which contains 6 grams of sodium nitrite and 12cos. of glacial acetic acid per litre. After diazotization for 15minutes, the yam is lifted.

rinsed, and soaped to shade as in Example 1- pling component and acompound selected from the group consisting of the free leuco compoundsof vat dyestuffs and the salts of the free leuco compounds of vatdyestuffs, and thereafter simultaneously effecting diazotization andcoupling and conversion or the leuco derivative to the parent vatdyestufl with nitrous acid.

2.Pi'ocess for the production-of mixed shades on textile materialscontaining organic derivatives of cellulose, which comprises applyingthereto a diazotizable amine, 'an arylamide of 2.3-oxynaphthoic acid,and a compound selected from the group consisting of the free leucocompounds ,5

of vat dyestuiis and the salts of the free leuco compounds of vatdyestuffs, and thereafter simultaneously effecting diazotization andcoupling and conversion of the leuco derivative to the par-- ent vatdyestui! with nitrous acid. 10 3. Process for the production of mixedshades on textile materials containing organic derivatives of cellulose,which comprises apply n to the materials a diazotizable amine, an azocoupling component, and a compound selected from the group 15 consistingof the free leuco compounds of vat dyestufi's and the salts of the freeleuco compounds of vat dyestuffs, and thereafter simultaneouslyeflecting diazotization and coupling and conversion of the leucoderivative to the parent vat dye- 20 stuff with nitrous acid.

4. Process for the production of mixed shades on textile materialscontaining cellulose acetate,

.which comprises applying thereto a diazotizable amine, a diacyl-acetylderivative of an; aromatic 25 diamine, and a compound selected from thegroupconsisting of .the free leuco compounds of vat dyestuifs and thesalts of the free leuco compounds of vat dyestuffs, and thereaftersimultaneously effecting diazotization' and coupling and 30 conversionof the leuco derivative to the parent vat dyestufl with nitrous acid.

5. Process for the production of mixed shades -on textile materialscontaining organic derivatives of cellulose, which comprises applying tothe 35 materials a diazotizable amine, an azo coupling component and acompound selected from the group consisting of the free leuco compoundsof anthraquinone vat dyestuffs containing a single anthraquinonenucleus, and the salts of said free 40 leuco compounds, and thereaftersimultaneously effecting diazotization and coupling and conversion ofthe leuco derivative to the parent vat azotizable amine, an an) couplingcomponent and a compound selected from the group consisting of the freeleuco compounds of anthraquinone vat 50 dyestuffs containing a singleanthraquinone nucleus, and the salts of said free leuco compounds, andthereaftersimultaneously efl'ecting diazotization and coupling andconversion of the leuco derivative to'the parent vat dyestuif withnitrous acid.

7. Process for the'production of mixed shades on textile materialscontaining cellulose acetate, which comprises applyi to the materials adiazotizable amine, a diacyl-acetyl derivative of an 00 aromaticdiamine, and a compound selected from the group consisting of'the freeleuco compounds of anthraquinone vat dyestufls containing a 1 gleanthraquinone nucleus and the salts of said free leuco compounds, andthereafter effecting di- 65 azotization and coupling simultaneously withconversion of the leuco derivative to the parent vat dyestuif withnitrous acid.

I above numbered patenflreg'uiring correction as follows:

. CERTIFICATE OIf'CORREGTION, Pateht -Np. Z-,.013 689 I 1 EkN sT WILLIAMKIRK, TYALL 4 It is hereby certified thatferror' appears in theprintedspecification of the Page-2, first cwlumn, .l 'ines 5 and 6, for -"U.S'Application S. No. 666,172" read British Patent-N0. 404,327; and thatthe said Letters Patent should be readwiththis correction therein thatthe same mayeonform 'tothe record (if the ease in the Patent Office.Signed and sealedthis 8th day" of OctOber AI 1935'. K

. 'r L'eslie Frazer (Seal) Acting Commissio er of Patents.

September 10, 1935.-

